CN103333370B - Organic and inorganic microcapsule coating expansible graphite preparation method - Google Patents
Organic and inorganic microcapsule coating expansible graphite preparation method Download PDFInfo
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- CN103333370B CN103333370B CN201310315318.4A CN201310315318A CN103333370B CN 103333370 B CN103333370 B CN 103333370B CN 201310315318 A CN201310315318 A CN 201310315318A CN 103333370 B CN103333370 B CN 103333370B
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Abstract
The invention relates to the field of microcapsule coating expansible graphite, and discloses an organic and inorganic microcapsule coating expansible graphite preparation method. The organic and inorganic microcapsule coating expansible graphite is a semi-transparent solid small particle which is white in appearance, and black inside, a capsule material is a polymer resin and inorganic compound dual-material component, and the average particle size of a capsule core is 50-200mu. m. The method comprises two steps of: step 1, depositing a layer of inorganic compound on the surface of the expansible graphite at first, wherein the inorganic compound is a flame retardant, and a synergistic flame retardant effect is improved through the inorganic compound and the expansible graphite when the coated expansible graphite is heated; and step 2, adopting resin as the capsule material to coat the expansible graphite through utilizing an in-situ polymerization method. After the coating, the compatibility of the expansible graphite and organic matters is obviously improved, the expansion rate of the expansible graphite can be improved, the flame retardant effect is improved, and moreover, the initial expanding temperature of the expansible graphite can also be increased, and accordingly, the flame retardant application scope of the expansible graphite is widened.
Description
Technical field
The invention belongs to microcapsule coated technical field, particularly a kind of method of fluoropolymer resin and the dual coated expansible black lead of mineral compound organic-inorganic.
Background technology
Along with the development and progression of society, in recent decades, macromolecule polymeric material obtains and develops rapidly, is widely applied in every field, its turnout increases year by year, day by day be applied to all respects such as national economy and people's lives, but most macromolecular material is all inflammable material, and then not easily puts out, a large amount of toxic smoke is had to produce during burning, serious threat is caused, so macromolecular material is fire-retardant becomes the focus of world attention to the life of the people and property.
Along with the research and development to fire retardant, phosphorous halogen fire retardant is replaced by without phosphorus halogen fire retardant, and wherein Intumescent Retardant System is nearest study hotspot, and expansible black lead is then the expansion type flame retardant received much concern in recent years.Expansible black lead (EG) is a kind of compound between graphite layers obtained after chemical oxidization method or electrochemical oxidation process process by natural flake graphite, and with regard to structure, EG is a kind of nanocomposite.Common H
2sO
4when by more than 200 DEG C high temperature, there is redox reaction between sulfuric acid and graphite carbon atom, produce a large amount of SO in the EG that oxidation obtains
2, CO
2and water vapour, make EG start to expand, and 900 DEG C time, reach maximum volume, 280 times when its final volume can reach initial.This characteristic makes EG can be increased fray-out of flame by the moment of volume when fire occurs.
C+H
2SO
4→CO
2+2H
2O+2SO
2
(Li ZM.et al, Journal of Applied Polymer Science, 2008,110 (6): 3871 such as Li Zhongming; PolymerInternational, 2006,55 (8): 862) have studied the impact that expansible black lead improves rigid polyurethane foam flame retardant properties, find that expansible black lead can effectively improve rigid polyurethane foam flame retardant properties, when the massfraction of expansible black lead is 30wt%, the limiting oxygen index(LOI) of polyurethane foamed material reaches 39.5.Because expansible black lead is inert substance, very poor with organism consistency, being added to as filler to cause the mechanical property of polymkeric substance to decline in superpolymer, such as: add the EG of 20wt% in RPUF after, its compressive strength drops to 8.9MPa from the 14.4MPa of pure RPUF, and modulus of compression also drops to 205.5MPa (Lei shi, et al.Polymer-Plastics Technology and Engineering from 258.6MPa, 2005,44:1323).And inorganic particulate and organic compatibility problem can well be solved by microcapsule coated, Chen Xu etc. adopt melamine resin to carry out microcapsule coated test as wall material to magnesium hydroxide powder, modified oxygen magnesium oxide significantly can improve the flame retardant properties of EVA, when the massfraction of magnesium hydroxide is 60%, vertical combustion from unmodified V-2 rank rise to V-0 level (Chen Xu etc. the preparation and application of magnesium hydroxide microcapsule. insulating material, 2009,42 (5): 14-23).The present invention improves EG and organic consistency by microcapsule coated method, by aluminium hydroxide and EG cooperative flame retardant, substantially increase flame retardant effect, and aluminium hydroxide can play certain restraining effect to smoke which, and, after coated, improve EG initial expansion temperature, expand the fire-retardant range of application of expansible black lead.
Summary of the invention
The object of the invention is to improve expansible black lead and organic consistency, simultaneously obtain the good and expansible black lead of good flame retardation effect of consistency with inorganic combustion inhibitor cooperative flame retardant.
1. the invention provides the preparation method of organic-inorganic microcapsule coated expansible black lead, it is characterized in that organic-inorganic microcapsule coated expansible black lead to be appearance be white, the translucent solid granule of inner black, capsule material is fluoropolymer resin and mineral compound, and capsule-core is expansible black lead.Processing step and the condition of the method are as follows:
1) 5 ~ 40 parts of expansible black leads are joined in 100 parts of water, and pass through ultrasonic apparatus ultrasonic disperse 30 ~ 120 minutes, then join in there-necked flask and stir, be heated to 50 ~ 80 DEG C, add 20 ~ 60g inorganic compound aqueous solution, stir 30 ~ 120 minutes, drip a certain amount of 10%Na
2cO
3the aqueous solution regulates pH to be 7 ~ 10, keeps stirring 1 ~ 3 hour;
2) 10 ~ 50g polymer resin solution is added in flask, and 50 ~ 80 DEG C of dispersed with stirring, stir after 5 ~ 30 minutes, then be cooled to room temperature, by acetic acid adjust ph 3 ~ 6, be slowly warming up to 50 ~ 80 DEG C, and stir 60 ~ 180 minutes, cooling, uses 10%Na
2cO
3the aqueous solution regulates pH to be 7 ~ 10;
3) by 2) in the mixture that obtains leave standstill 6 ~ 12 hours, then suction filtration, washing, dries under 60 DEG C of conditions, can obtain the expansible black lead of organic-inorganic microcapsule coated.
2. the preparation method of a kind of organic-inorganic microcapsule coated expansible black lead according to claim 1, the resin that it is characterized in that using in the method is terpolycyantoamino-formaldehyde resin, one or more in urethane and methylbenzene e pioic acid methyl ester, resol, polyureas, furfuryl alcohol resin, polymeric amide, urethane, aniline resin, ketone resin, epoxy resin and Synolac.
3. the preparation method of a kind of organic-inorganic microcapsule coated expansible black lead according to claim 1, the inorganic coating material that it is characterized in that using in the method is aluminium hydroxide, magnesium hydroxide and zinc borate one or more.
4. the preparation method of a kind of organic-inorganic microcapsule coated expansible black lead according to claim 1, expansible black lead ultrasonic time was excellent with 60 ~ 90 minutes.
5. the preparation method of a kind of organic-inorganic microcapsule coated expansible black lead according to claim 1, is characterized in that mixture whipping temp preferably 60 ~ 70 DEG C.
6. the preparation method of a kind of organic-inorganic microcapsule coated expansible black lead according to claim 1, the median size of expansible black lead is 50 ~ 200 μm.
The present invention compared with prior art, has following advantage:
1, at expansible black lead surface deposition inorganic combustion inhibitor, inorganic combustion inhibitor can carry out cooperative flame retardant with expansible black lead, to improve the flame retardant properties of material, and, adding by inorganic combustion inhibitor, the effect pressing down cigarette can be played.
2, using resin as capsule material, not only can improve expansible black lead and organic consistency, the expanding volume of expansible black lead can also be improved simultaneously, improve the initial expansion temperature of expansible black lead simultaneously.
3, method technique provided by the invention is simple, and strong operability, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is that in example 1 of the present invention, expansible black lead shows deposition aluminium hydroxide electron scanning micrograph.
Fig. 2 is terpolycyantoamino-formaldehyde resin and the dual coated expansible black lead electron scanning micrograph of aluminium hydroxide in example 2 of the present invention.
Fig. 3 is terpolycyantoamino-formaldehyde resin and aluminium hydroxide dual coated front and back expansible black lead thermal weight loss in example 3 of the present invention.
Fig. 4 is terpolycyantoamino-formaldehyde resin and aluminium hydroxide dual coated front and back FTIR spectrogram in example 2.
Embodiment
Provide specific embodiment below to be described further technical scheme of the present invention; but what deserves to be explained is that following instance can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field according to the content of foregoing invention, to the present invention do some non-intrinsically safes improvement and adjustment still belong to protection scope of the present invention.
Example 1
1) expansible black lead being 100 μm by 5 parts of median sizes joins in 100 parts of water, and by the ultrasonic 60min of ultrasonic apparatus, then joins in there-necked flask and stir, be heated to 50 DEG C, add 20g aluminum sulfate aqueous solution, stirs 30min, drips a certain amount of 10%Na
2cO
3the aqueous solution regulates pH to be 7, keeps stirring 1.5 hours;
2) added in flask by 40 parts of terpolycyantoamino-formaldehyde resin solution, and 50 DEG C of dispersed with stirring, after stirring 15min, be then cooled to room temperature, by acetic acid adjust ph 3, be slowly warming up to 50 DEG C, and stir 60min, cooling, uses 10%Na
2cO
3the aqueous solution regulates pH to be 7;
3) by 2) in the mixture that obtains leave standstill 6h, then suction filtration, washing, dries under 60 DEG C of conditions, can obtain the expansible black lead that melamino-formaldehyde-aluminium hydroxide is coated.
Example 2
1) expansible black lead being 50 μm by 5 parts of median sizes joins in 100 parts of water, and by the ultrasonic 30min of ultrasonic apparatus, then joins in there-necked flask and stir, be heated to 50 DEG C, add 30 parts of aluminum sulfate aqueous solutions, stirs 30min, drips a certain amount of 10%Na
2cO
3the aqueous solution regulates pH to be 8, keeps stirring 2 hours;
2) added in flask by 20 parts of terpolycyantoamino-formaldehyde resin solution, and 60 DEG C of dispersed with stirring, after stirring 20min, be then cooled to room temperature, by acetic acid adjust ph 4, be slowly warming up to 60 DEG C, and stir 90min, cooling, uses 10%Na
2cO
3the aqueous solution regulates pH to be 8;
3) by 2) in the mixture that obtains leave standstill 6h, then suction filtration, washing, dries under 60 DEG C of conditions, can obtain the expansible black lead that melamino-formaldehyde-aluminium hydroxide is coated.
Example 3
1) expansible black lead being 200 μm by 30 parts of median sizes joins in 100 parts of water, and by the ultrasonic 90min of ultrasonic apparatus, then joins in there-necked flask and stir, be heated to 65 DEG C, add 40 parts of aluminum sulfate aqueous solutions, stir 120min, drip a certain amount of 10%Na
2cO
3the aqueous solution regulates pH to be 8.5, keeps stirring 3 hours;
2) added in flask by 30g terpolycyantoamino-formaldehyde resin solution, and 65 DEG C of dispersed with stirring, after stirring 30min, be then cooled to room temperature, by acetic acid adjust ph 4.5, be slowly warming up to 65 DEG C, and stir 120min, cooling, uses 10%Na
2cO
3the aqueous solution regulates pH to be 8.5;
3) by 2) in the mixture that obtains leave standstill 6h, then suction filtration, washing, dries under 60 DEG C of conditions, can obtain the expansible black lead that melamino-formaldehyde-aluminium hydroxide is coated.
Claims (2)
1. organic-inorganic microcapsule coated expansible black lead, it is characterized in that organic-inorganic microcapsule coated expansible black lead to be appearance be white, capsule material is fluoropolymer resin and mineral compound, and capsule-core is the translucent solid granule of black, capsule-core is 50 ~ 200 μm of expansible black leads
Processing step and the condition of preparing organic-inorganic microcapsule coated expansible black lead are as follows:
1) by 5 ~ 40 parts (with water be 100 parts as a reference) expansible black lead joins in 100 parts of water, and pass through ultrasonic apparatus ultrasonic disperse 30 ~ 120 minutes, then join in there-necked flask and stir, be heated to 50 ~ 80 DEG C, add 20 ~ 60g inorganic compound aqueous solution, stir 30 ~ 120 minutes, drip a certain amount of 10%Na
2cO
3the aqueous solution regulates pH to be 7 ~ 10, keeps stirring 1 ~ 3 hour;
2) 10 ~ 50 parts of polymer resin solution are added in flask, and 50 ~ 80 DEG C of dispersed with stirring, stir after 5 ~ 30 minutes, then be cooled to room temperature, by acetic acid adjust ph 3 ~ 6, be slowly warming up to 50 ~ 80 DEG C, and stir 60 ~ 180 minutes, cooling, uses 10%Na
2cO
3the aqueous solution regulates pH to be 7 ~ 10;
3) by 2) in the mixture that obtains leave standstill 6 ~ 12 hours, then suction filtration, washing, dries under 60 DEG C of conditions, can obtain the expansible black lead of organic-inorganic microcapsule coated;
Wherein, the resin of use be terpolycyantoamino-formaldehyde resin, one or more in resol, polyureas, furfuryl alcohol resin, polymeric amide, urethane, aniline resin, ketone resin, epoxy resin and Synolac; The inorganic coating material used is aluminium hydroxide.
2. organic-inorganic microcapsule coated expansible black lead according to claim 1, expansible black lead ultrasonic time was excellent with 60 ~ 90 minutes.
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| CN104959085A (en) * | 2015-05-07 | 2015-10-07 | 温州生物材料与工程研究所 | Size and shape controllable polyelectrolyte hollow microcapsule and application thereof |
| CN104829796B (en) * | 2015-05-18 | 2017-02-22 | 齐齐哈尔大学 | Preparation method of flame retardant for plastics |
| CN105504115B (en) * | 2015-12-18 | 2018-05-18 | 武汉轻工大学 | Eliminate the microcapsule method in situ that carbon black or graphite inhibit effect in Polystyrene heat insulation material synthesis |
| CN107345002B (en) * | 2016-05-06 | 2019-05-24 | 武汉理工大学 | A kind of expansible graphite fire retardant of hydroxide β-cyclodextrin and preparation method thereof |
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| CN107641221B (en) * | 2016-07-22 | 2019-08-23 | 武汉理工大学 | A kind of hydroxide-modified expansible graphite fire retardant and preparation method thereof |
| CN108102142B (en) * | 2017-12-08 | 2019-10-11 | 中国科学院化学研究所 | A kind of the expansible graphite fire retardant and preparation method of surface encapsulated nanoparticles |
| CN109180999A (en) * | 2018-08-16 | 2019-01-11 | 浙江蓝盾电工新材料科技有限公司 | A kind of graphite oxide promotees dispersing agent and fire extinguisher filler preparation method |
| CN110681401A (en) * | 2019-05-28 | 2020-01-14 | 济南大学 | Preparation method of expanded graphite carbon-based solid acid catalyst |
| CN112495318A (en) * | 2020-12-22 | 2021-03-16 | 南京工业大学 | Double-layer microcapsule flame retardant and preparation method thereof |
| CN113429632B (en) * | 2021-07-19 | 2022-07-08 | 青岛科技大学 | High-thermal-conductivity expandable graphite microcapsule and preparation method and application thereof |
| CN115093832B (en) * | 2022-06-09 | 2023-07-25 | 武汉中科先进材料科技有限公司 | Preparation method of environment-friendly heat-insulating temperature-controlling flame-retardant material |
| CN116426236B (en) * | 2023-03-07 | 2023-12-15 | 永一胶粘(中山)有限公司 | Flame-retardant adhesive and preparation method and application thereof |
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| CN102140184A (en) * | 2011-01-18 | 2011-08-03 | 四川大学 | Composite flame retardant with core-shell structure and preparation method thereof |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102140184A (en) * | 2011-01-18 | 2011-08-03 | 四川大学 | Composite flame retardant with core-shell structure and preparation method thereof |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
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